US7727401B2 - Selective purification of mono-terpenes for removal of oxygen containing species - Google Patents

Selective purification of mono-terpenes for removal of oxygen containing species Download PDF

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US7727401B2
US7727401B2 US10/984,108 US98410804A US7727401B2 US 7727401 B2 US7727401 B2 US 7727401B2 US 98410804 A US98410804 A US 98410804A US 7727401 B2 US7727401 B2 US 7727401B2
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column
oxygen
containing impurity
cineole
contacting
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US20060100470A1 (en
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Heather Regina Bowen
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Versum Materials US LLC
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Air Products and Chemicals Inc
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Priority to TW094138767A priority patent/TWI265043B/zh
Priority to KR1020050106552A priority patent/KR100786605B1/ko
Priority to EP05024304A priority patent/EP1655355B1/de
Priority to DE602005019669T priority patent/DE602005019669D1/de
Priority to AT05024304T priority patent/ATE459401T1/de
Priority to JP2005324645A priority patent/JP2006137754A/ja
Priority to CNA200510138062XA priority patent/CN1800125A/zh
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
    • C09F3/00—Obtaining spirits of turpentine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J20/282—Porous sorbents
    • B01J20/283—Porous sorbents based on silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B01D15/20—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
    • B01D15/203—Equilibration or regeneration

Definitions

  • Alpha-terpinene as an example, is extracted from wood chips and is commercially available at its highest purity at around 90% (all % herein are vol. %). At the highest available purity, it still contains four main impurities, with Eucalyptol (1,8-Cineole) ranging from 1-5%.
  • GB 194286 discloses that essential oils and terpene hydrocarbons are purified by treatment with a suitable material which reacts with the impurities present, then adding an “agglomerating agent,” and finally removing the solid substances.
  • agents for acting upon the impurities “active” halogen compounds, such as alkali or alkaline earth hypochlorites are mentioned, fuller's earth, silica gel, boneblack or other decolorizing charcoal are given as examples of the “agglomerating agents”; while the starting materials specified are oils of copaiba, fir cones, ginger, juniper, pepper, pine, cedar and peppermint, as well as pinene, dipentene, limonene and isoprene.
  • This process uses water in the separation process and reacts the sulfur containing compounds which cause odor before agglomerating the reacted compounds on materials such as silica gel before mechanical separation of the desired turpentine product.
  • the present invention overcomes the deficiencies of the prior art in purifying mono-terpenes of oxygen-containing impurity compounds without the requirement for the use of additional chemical reagents or elution solvents so as to recover a neat product and recognizing the particular detriment of such oxygen-containing impurity compounds in electronic materials use, as will be set forth in greater detail below.
  • the present invention is a method for preparing mono terpenes as porogens for porous silicon oxide dielectric film depositions in electronic devices by separating oxygen-containing impurity compounds from mono terpenes, comprising;
  • FIG. 1 is a schematic process flow diagram of a preferred embodiment of the present invention for purifying mono-terpenes of oxygen-containing impurity compounds using silica gel column chromatography.
  • FIG. 2 is a graph showing breakthrough curves at the downstream end of silica gel packed column 52 showing Eucalyptol Runs # 1 and # 2 are effectively held up on the silica gel column until a sharp final breakthrough in contrast to the steadystate passage of non-oxygen-containing mono terpenes.
  • FIG. 3 is a graph showing the product elution at the downsteam end of the activated silica gel column 52 for one individual run of the system demonstrating purity improvements in the alpha-Terpinene product stream with the removal of the Eucalyptol impurity.
  • the present invention is a novel process that was developed to purify preferably C 10 H 16 mono-terpenes, which are useful as porogens in porous silicon oxide dielectric film deposition processes using silicon oxide precursors, such as diethoxymethylsilane (DEMS) for manufacture of integrated circuits for electronic device fabrication;
  • silicon oxide precursors such as diethoxymethylsilane (DEMS) for manufacture of integrated circuits for electronic device fabrication
  • alpha-Terpinene and d-Limonene Two porogens that are commonly used are alpha-Terpinene and d-Limonene. Both porogen species are extracted from natural products, wood chips and citrus peels respectively and contain several impurities of varying levels. Commercially available grades of these materials are typically quite poor, compared to typical semiconductor precursors, as the main usage is for flavor and aroma products.
  • Alpha-Terpinene purity varies from 90-95% for the highest quality material on the market and contains four major impurities: alpha-Phellandrene (C 10 H 16 ), d-Limonene (C 10 H 16 ), para-Cymene (C 10 H 14 ) and 1,8-Cineole (Eucalyptol) or possibly 1,4-Cineole
  • the mono-terpene desired for the present invention is used as a pore generator with a silicon matrix during dielectric film deposition for electronic device manufacture such as integrated circuit fabrication, and during post film processing, the porogen component is removed. All of the above-recited impurities, except 1,8-Cineole or possibly 1,4-cineole, would function as a replacement for alpha-Terpinene, maintaining a similar pore size and distribution.
  • Eucalyptol an ether bridged oxygen species, C 10 H 18 O
  • C 10 H 18 O an ether bridged oxygen species
  • All of the components have the same boiling point (175-176° C.) and are not separable by distillation.
  • D-Limonene extracted from orange peels, also contains some oxygen containing species, such as Linalool (C 10 H 18 O) and Octanal (C 8 H 16 O), that would have an effect on the DEMS dielectric film deposition process for electronic device applications. Trials were conducted with different media to evaluate the effectiveness of removing the impurities.
  • Alpha-Terpinene as an example, is extracted from wood chips and is commercially available at its highest purity at around 90%. At the highest available purity it still contains four main impurities, with 1,8-Cineole ranging from 1-5%. Traditional methods for removing the impurities, such as distillation, would not be effective due to the similar boiling points of the desired product and all of the impurities (175-176° C.).
  • activated silica gel allows an efficient separation of the non-oxygen containing species from the oxygen-containing impurity compounds, such as Eucalyptol.
  • oxygen-containing impurity compounds such as Eucalyptol.
  • activated silica gel was able to reduce 1,8-Cineole levels from 3.45% to approximately 0.024% in activated silica gel column-treated alpha-Terpinene.
  • the proposed mechanism for this selective purification is that the bridged oxygen species found as oxygen-containing impurity compounds in the mono-terpenes are susceptible to hydrogen bonding on the activated silica gels' —SiOH terminal groups.
  • the activated silica gel also demonstrates a high affinity to remove free water in the mono terpene stream left over from steam distillation.
  • the terminal hydroxyl groups on the silica gel will retain polar molecules, such as free water and the oxygen-containing impurity compounds preferentially over the non-oxygen containing desired terpenes, before an unexpectedly sharp breakthrough of the oxygen-containing impurity compounds occurs from the activated silica gel column.
  • the silica gel column When breakthrough of the oxygen-containing impurity compound, Eucalyptol, is detected in the silica gel column effluent, the silica gel column is regenerated by first draining the liquid from the silica gel column and then running a low molecular weight alcohol, such as; ethanol, propanol, isopropanol in reverse flow direction (countercurrent to mono terpene feed flow) to displace the bound oxygen-containing impurity compound material.
  • a low molecular weight alcohol such as; ethanol, propanol, isopropanol in reverse flow direction (countercurrent to mono terpene feed flow) to displace the bound oxygen-containing impurity compound material.
  • the vapor pressure of the alcohol is quite high compared to the terpene and can be driven off under vacuum. High temperature reactivates the Si—OH terminal groups of the activated silica gel for the next purification run.
  • Eucalyptol is an undesirable impurity in the alpha-Terpinene due to its structural differences.
  • PECVD plasma-enhanced chemical vapor deposition
  • the ether oxygen in the Eucalyptol breaks and links with the silicon source (DEMS) forming a strong Si—O bond.
  • DEMS silicon source
  • the objective of the terpene is as a pore generator in the porous dielectric film and then to be removed from the film after pore formation during the post treatment process, the formation of the Si—O—C— bond between DEMS and Eucalyptol results in a “filled” pore, where the porogen is integrated into the silicon matrix and cannot be removed. This directly adversely effects the dielectric constant of the film with increased retained carbon and a changed pore distribution.
  • alpha-terpinene is a natural product
  • the Eucalyptol levels vary depending on the wood stock feed used. Having unpredictable Eucalyptol levels prevents a reproducible porous dielectric film manufacturing process for the integrated circuit or electronic materials fabricators, as each batch of alpha-Terpinene used integrates different amounts of “filled” pores and variable amount of carbon, based upon the Eucalyptol levels. This degree of variability is highly unacceptable to the exacting requirements of the electronic device fabricating industry, which operates with extremely tight dimensions and precise physical and electrical properties of precursor materials. Significantly reducing the Eucalyptol and other oxygen-containing impurity compound levels in the terpene feed allows for a more definable electronic device fabrication process with consistent dielectric film results.
  • a preferred embodiment of the purification process of the present invention is exemplified with reference to FIG. 1 , as follows: a stainless steel column 52 is packed with Davisil silica gel and regenerated under a heated vacuum cycle to remove surface bound water. The column 52 is allowed to cool to room temperature. The system is operated as a pressure push to vent system with the pressure drop occurring at valve 28 . Neat mono-terpene (alpha-Terpinene or d-Limonene) containing oxygen-containing impurity compounds is pushed up the column 52 from a source container 60 using a pressure above atmospheric to 100 psig from an inert push gas source 66 .
  • the terpene product depleted of oxygen-containing impurity compounds is removed through valve 22 , line 24 , filtered through filter 26 , flow is metered through valve 28 , line 30 , valve 32 and 38 to be collected in purified terpene product container 40 receiving terpene through diptube 44 with pressure relieved to a vent through valve 46 .
  • the terpene product can be drawn off through valve 34 into a customer-use vessel for use as the porogen in the porous dielectric film deposition process for electronic materials manufacture in electronic device fabrication. Production can be monitored by scale 42 and pressure gauge 50 . Pressure can be regulated in part by valve 48 .
  • the material collected off the top (product or downstream end) of the column 52 is periodically sampled through sample valve 34 and sample line 36 to monitor when the impuritiy level of the oxygen-containing impurity compound starts to rise (break-through). Collection is then stopped. Liquid in the column 52 is drained through valve 54 into a separate mono terpene collection container 68 (column drains) through valve 74 and diptube 70 as it contains high levels of the impurity. This can be periodically removed through valve 74 for further processing through the system. Container 68 may be vented through valve 72 , if necessary.
  • neat alcohol from alcohol source container 14 is dispensed in diptube 16 and valve 18 by inert push gas source 10 through valve 12 and is passed through line 20 and valve 22 down the column 52 countercurrent to the production flow of terpene to displace the oxygen-containing impurity compound from the column through valve 54 , line 76 , valve 78 and diptube 82 into oxygen-containing impurity compound receiving container 80 .
  • Container 80 can be vented through valve 84 . If desirable, the pure alcohol can be recovered from flush container 80 through normal distillation techniques to refill container 14 for further use. Since the vapor pressure of the alcohol is quite high compared to the terpenes, the column 52 can be easily regenerated under vacuum and heated to drive off the alcohol. Once cool, the column 52 is ready for the next run.
  • the activated silica gel has terminal hydroxyl groups that are good for hydrogen bonding of selective species.
  • the terminal groups will hold polar molecules, such as free water and the oxygen containing species, preferentially over the non-oxygen containing terpenes. Since the forces holding the oxygen containing species are relatively weak, they are easy to displace during regeneration by the low molecular weight and more polar alcohol, but strong enough to hold the oxygen terpene to the gel during the purification runs without significant desorption.
  • Silica gel contains terminal hydroxyl groups on the surface. These groups are hydrophilic and have a propensity to bond polar molecules. Using this effect, hydrogen bonding, the oxygen bridged species is selectively removed from the mono-terpene as the raw material is passed through the column. Eucalyptol continues to be removed from the mass transfer zone (the silica gel packed column) until the media is saturated and the impurity breaks through into the effluent.
  • the silica gel also has a high affinity for trace moisture in the product (residual from steam distillation) and can remove free moisture at 500 ppm levels to below 40 ppm.
  • the impurity has a high affinity for the media
  • another polar molecule is used to desorb it from the media.
  • a low molecular weight alcohol is used, ethanol or isopropanol.
  • the solvent is then readily stripped out of the column under vacuum and under heat to regenerate the bed, again leaving free terminal hydroxyl groups, ready for the next purification run.
  • alpha Terpinene with a starting percentage of 2.36% Eucalyptol passing through the silica gel column can reduce the level to below detectable limits by a flame ionization detector (FID) on a gas chromatograph.
  • FID flame ionization detector
  • a column packed with 927 cubic centimeters of silica gel is able to purify 5 kilograms of alpha-Terpinene with no Eucalyptol present in the collect terpene fraction
  • the mass ratio between feed material to gel with 2.4% Eucalyptol is 6.6:1 to reduce below 0.05% and 4:1 for 0% Eucalyptol.
  • Flow rate of the feed through the system was 100 grams per minute.
  • Chromatography of the terpene, at room temperature, allows for selective removal of the oxygen containing impurity compound from the liquid phase.
  • the present invention allows for significant purity improvement to the final product, with typical alpha-Terpinene purities at greater than 97% after column purification, with the other impurities acting as similar porogen placeholders.
  • Advantage of this process is that the mono-terpene is purified neat without the use of a carrier solvent or the need for a reverse phase solvent. Removing the oxygen-containing impurity compounds significantly reduces the likelihood that the porogen becomes entrapped in the silicon matrix during the plasma deposition process, reducing the number of filled pores and the amount of entrained carbon.
  • FIG. 2 graph shows the unexpected results of the present invention in dramatically, selectively removing the Eucalyptol oxygen-containing impuritiy compound with minimal change to the starting percentage of the product terpenes.
  • the graph shows a sharp breakthrough of Eucalyptol, making the operation of the separatory process of the present invention convenient and operable on a commercial scale, wherein production of the desired mono-terpenes is unaffected by the silica gel column packing, while the oxygen-containing impurity compounds are effectively bound by the silica gel column packing up until the time for regeneration of the column with alcohol.
  • FIG. 3 details the result of a single purification run.
  • Alpha-Terpinene with a starting purity of 95.7% was passed through a regenerated column using a 7 psig inert gas push and a flow rate of 100 grams per minute. After an initial elution of the previous runs material out of the filter, the process stabilizes after the first 0.1 kg collected.
  • Alpha-Terpinene purity rises conjointly with the removal of Eucalyptol from the feed steam. Overall, alpha-Terpinene purity was increased to 98.1%. Again, as with FIG.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Gas Separation By Absorption (AREA)
US10/984,108 2004-11-09 2004-11-09 Selective purification of mono-terpenes for removal of oxygen containing species Active 2028-02-03 US7727401B2 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US10/984,108 US7727401B2 (en) 2004-11-09 2004-11-09 Selective purification of mono-terpenes for removal of oxygen containing species
TW094138767A TWI265043B (en) 2004-11-09 2005-11-04 Selective purification of mono-terpenes for removal of oxygen containing species
KR1020050106552A KR100786605B1 (ko) 2004-11-09 2005-11-08 산소 함유 화학종을 제거하기 위한 모노테르펜의 선택적정제 방법
EP05024304A EP1655355B1 (de) 2004-11-09 2005-11-08 Selektive Reinigung von Monoterpen zur Entfernung Sauerstoff enthaltender Komponenten
DE602005019669T DE602005019669D1 (de) 2004-11-09 2005-11-08 Selektive Reinigung von Monoterpen zur Entfernung Sauerstoff enthaltender Komponenten
AT05024304T ATE459401T1 (de) 2004-11-09 2005-11-08 Selektive reinigung von monoterpen zur entfernung sauerstoff enthaltender komponenten
JP2005324645A JP2006137754A (ja) 2004-11-09 2005-11-09 酸素含有種を除去するためのモノテルペンの選択的精製
CNA200510138062XA CN1800125A (zh) 2004-11-09 2005-11-09 选择纯化单萜烯以除去含氧物质

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US10/984,108 US7727401B2 (en) 2004-11-09 2004-11-09 Selective purification of mono-terpenes for removal of oxygen containing species

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AT (1) ATE459401T1 (de)
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EP2004872A1 (de) * 2006-03-31 2008-12-24 L'AIR LIQUIDE, S.A. pour l'étude et l'exploitation des procédés Georges Claude Neue zusammensetzung porenbildender vorläufer und daraus erhaltene poröse dielektrische schichten
GB0624807D0 (en) * 2006-12-13 2007-01-24 Ineos Fluor Holdings Ltd Process
US8753986B2 (en) 2009-12-23 2014-06-17 Air Products And Chemicals, Inc. Low k precursors providing superior integration attributes
CN111363624B (zh) * 2020-03-26 2022-06-21 华东理工大学 一种精油脱萜烯的方法
CN120290253B (zh) * 2025-04-15 2026-01-30 江苏嘉福制药有限公司 一种天然桉油的精炼方法及其应用

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US2316299A (en) * 1939-01-25 1943-04-13 Thompson Archibald Walter Dielectric composition
US2585492A (en) * 1949-04-14 1952-02-12 Sun Oil Co Continuous adsorption process
US2723756A (en) * 1951-04-24 1955-11-15 John M Miller Apparatus with bonded adsorbent block and capillary chromatographic adsorption therewith
US2930821A (en) * 1955-11-29 1960-03-29 Neville Chemical Co Recovery of high purity indene by chromatographic fractionation and fractional distillation
US3546256A (en) * 1962-02-01 1970-12-08 Exxon Research Engineering Co Process for separating organic mixtures containing nf2 groups
US3305591A (en) * 1963-05-08 1967-02-21 Colgate Palmolive Co Resolution of terpene alcohols by elution chromatography using optically active polymr
US3558732A (en) 1969-05-12 1971-01-26 Universal Oil Prod Co Aromatic hydrocarbon separation by adsorption
US3625733A (en) * 1969-05-16 1971-12-07 Owens Illinois Inc Substrate coating process
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DE602005019669D1 (de) 2010-04-15
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TWI265043B (en) 2006-11-01
US20060100470A1 (en) 2006-05-11
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EP1655355B1 (de) 2010-03-03
CN1800125A (zh) 2006-07-12

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